CN115975200A - Anchoring agent for silicone oil release agent and using method thereof - Google Patents
Anchoring agent for silicone oil release agent and using method thereof Download PDFInfo
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- CN115975200A CN115975200A CN202211685336.7A CN202211685336A CN115975200A CN 115975200 A CN115975200 A CN 115975200A CN 202211685336 A CN202211685336 A CN 202211685336A CN 115975200 A CN115975200 A CN 115975200A
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- release agent
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- mold release
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Abstract
The application relates to the technical field of release agent auxiliary materials, in particular to an anchoring agent for a silicone oil release agent and a preparation method thereof. The anchoring agent for the silicone oil release agent is a product obtained by jointly hydrolyzing raw materials at least comprising vinyl trialkoxysilane and glycidoxypropyltrialkoxysilane, wherein the molar ratio of the vinyl trialkoxysilane to the glycidoxypropyltrialkoxysilane is 1: 1.0-1.2. The yield of the silicone oil type release agent is 0.5-1.5% of the mass of the release agent. The anchoring agent for the silicone oil release agent does not contain acetoxyl, safety is greatly improved, the anchoring agent can be applied to the field of food packaging, and the anchoring effect of the anchoring agent is improved to a certain extent compared with the prior art.
Description
Technical Field
The application relates to the technical field of release agent auxiliary materials, in particular to an anchoring agent for a silicone oil release agent and a preparation method thereof.
Background
The silicone oil type release agent is a release agent which is widely used at present, and has good durability and no need of a solvent due to simple preparation conditions, good adhesion and separation, and is widely applied to daily chemical products.
When the release agent is coated on materials such as PET, PP, PE and the like, the surface of the release agent is poor in bonding performance with silicone oil, and the release agent can fall off even be transferred to the surface of the pressure-sensitive adhesive after being stored for a long time, so that the use of the pressure-sensitive adhesive is influenced. In order to adjust the properties of the silicone oil type release agent, various additives are required to be added into the release agent, wherein the anchoring agent is an additive for improving the adhesion between the release agent and the substrate, so that the release agent has a longer service life.
The commonly used anchoring agent at present is a composition of vinyl triacetoxysilane and glycidoxypropyltrimethoxysilane or a reaction product thereof, but the anchoring agent contains acetoxy and is not suitable for being used in the food industry.
Disclosure of Invention
The application provides an anchoring agent for silicone oil type mold release and a use method thereof, and acetoxyl is not contained in the anchoring agent for silicone oil mold release in the application, so that the safety is greatly improved, the anchoring agent can be applied to the field of food packaging, and the anchoring effect of the anchoring agent is improved to a certain extent compared with the prior art.
The anchoring agent for the silicone oil release agent is a product obtained by jointly hydrolyzing raw materials at least comprising a combination of vinyl trialkoxysilane and glycidoxypropyl trialkoxysilane, wherein the molar ratio of the vinyl trialkoxysilane to the glycidoxypropyl trialkoxysilane is 1: 1.0-1.2.
In the technical scheme of the application, hydrolysis products of vinyl trialkoxysilane and glycidoxypropyltrialkoxysilane, in which silicon hydroxyl compounds, dimer compounds or oligomer compounds are contained, are mainly used as the main components of the anchoring agent. The silicon hydroxyl compound can improve the adhesive force and has good adhesive property with the base material, and the dimer and the oligomer system can fix the silicon hydroxyl compound between the interface of the release agent and the base material, so that the silicon hydroxyl compound and the base material jointly have the anchoring effect. If the two silanes are directly added into the release agent without primary hydrolysis, the two silanes are easy to react with the pressure-sensitive adhesive interface in the curing process, so that the adhesion of the release agent is reduced, and the adhesive force loss of the pressure-sensitive adhesive is caused.
Preferably, in the hydrolysis reaction, the ratio of the amount of the water system to the mass of the vinyltrialkoxysilane is 8-10 mL: 1mol.
Preferably, the vinyltrialkoxysilane is any one of vinyltrimethoxysilane and vinyltriethoxysilane, and more preferably vinyltriethoxysilane.
Preferably, the glycidoxypropyltrialkoxysilane is glycidoxypropyltrimethoxysilane.
Preferably, the anchoring agent further comprises a water-insoluble cellulose having a viscosity of not higher than 10000cps. The water-insoluble cellulose is preferably ethyl cellulose ether. More preferably, the mass of the water-insoluble cellulose is 0.05 to 0.5 times that of a product obtained by co-hydrolyzing a raw material of a combination of vinyltrialkoxysilane and glycidoxypropyltrialkoxysilane.
Preferably, the vinyltrialkoxysilane and glycidoxypropyltrialkoxysilane are co-hydrolyzed under the following conditions: the reaction temperature is 40-60 ℃, the reaction time is 1-2 h, the pH is controlled to be 10.0-13.0 in the reaction process, and the solvent is removed after the reaction is finished.
Preferably, the pH is controlled to be 12.2 to 12.8 during the process.
Preferably, during the hydrolysis, methyltrimethoxysilane is also added, and the molar ratio of the methyltrimethoxysilane to the vinyl trialkoxysilane is 0.01-0.05: 1.
The application also relates to a using method of the anchoring agent for the silicone oil release agent, which is applied to various silicone oil release agents, and the using amount of the anchoring agent is 0.5-1.5 mt% of the total amount of the release agent.
Within the above range, the release agent can be more firmly attached to the surface of the substrate by the anchoring agent, and the molecular exchange between the release agent and the adhesive is less, so that the adhesive is less affected. And can still exert better effect in the high-temperature and high-humidity environment commonly used by food.
Detailed Description
The technical solution of the present application is further explained by the following specific embodiments.
In the following examples, the properties of the release agents are characterized by the following experiments:
1. release force: specifically referring to GB/T25256-2010 optical function film-release film 180-degree peeling force and residual adhesion rate test method, the property of the release agent is determined by adopting a mode of a PET release film peeling force tester to measure the peeling strength of the release agent, wherein the thickness of the release film after the release agent is coated is 0.019mm. When no release agent is used, the release force obtained by measurement is
2. Residual stress from the release force: as in experiment 1, the residual stress after the pressure-sensitive adhesive was peeled off from the release agent was measured, and the ratio of the residual stress to the original stress of the pressure-sensitive adhesive bag was calculated.
3. Adhesion performance of the release agent: the determination is carried out by adopting a grid marking method, which is specifically carried out according to GB/T9286-2021 colored paint and varnish marking test, and a PET film is selected as a base material.
4. Heat resistance and moisture resistance: the pressure sensitive adhesive, release agent, and substrate were left under the specified conditions, and then the measurements of experiment 1 and experiment 2 were repeated.
Embodiment 1 relates to an anchoring agent for a silicone oil release agent, and the preparation method is as follows:
preparing an aqueous solution of sodium bicarbonate, adjusting the pH to 8.0 for later use, adding vinyltrimethoxysiloxane and glycidoxypropyltrimethoxysilane into a reaction bottle, dropwise adding the prepared aqueous solution, reacting at 60 ℃ for 2 hours, and distilling under reduced pressure to remove the solvent after the reaction. Wherein the mass of the vinyl trimethoxy silane is 1.48g, and the mass of the glycidoxypropyl trimethoxy silane is 2.36g. Wherein the amount of the sodium bicarbonate aqueous solution is 0.1mL.
After the reaction is finished, the mixture is mixed with ethyl cellulose ether N10 according to the mass ratio of 5: 1 to be used as an anchoring agent.
In examples 2 to 14, optimum reaction conditions were selected by adjusting the pH, temperature and reaction time of the reaction based on example 1, and the specific reaction conditions are shown in Table 1.
TABLE 1 adjustment of hydrolysis reaction conditions
Example 15 differs from example 4 in that the amount of aqueous sodium bicarbonate solution used was 0.08mL.
The release agents prepared in examples 1 to 15 exhibited the performances in experiments 1 to 3 shown in table 2. The release agent is selected from a commercial GS5005 condensed type release agent with the viscosity of 1200cps, and the preparation formula is as follows:
g5005 condensed type release agent: 100 parts of (A);
120# solvent oil: 1900 parts;
and (3) antifogging agent: 50 parts of a mixture;
organotin catalyst: and 2 parts.
On the basis of the above, the anchoring agent in the following examples of the present application was added in an amount of 0.1% by mass of the release agent.
The release agent had a peel strength of 0.270N/mm, as determined without the addition of an anti-fogging agent.
Table 2 and Experimental results of examples 1 to 14
Wherein, the control group A is used as an anchoring agent after the mass of the vinyltrimethoxysilane and the mass of the glycidoxypropyltrimethoxysilane are directly mixed according to the proportion of the example 1.
Control B, epoxypropoxypropyltrimethoxysilane equimolar as compared to example 1, was replaced with vinyltriethoxysilane.
Control group C, in comparison with example 1, vinyltrimethoxysilane and the like were replaced by glycidoxypropyltrimethoxysilane
The experimental data prove that the hydrolysate system prepared by the method can exert good anchoring effect within the range of pH value of 10-12 and reaction temperature of 40-60 ℃. The above-mentioned hydrolysates comprise, on the one hand, silanol systems and, on the other hand, also oligomeric silanes. On one hand, the organic silicon oligomer and the non-water-soluble cellulose ether do not have molecular groups interacting with the pressure-sensitive adhesive, and have no obvious influence on the property of the pressure-sensitive adhesive, so that the release performance of the release agent is not influenced. On the other hand, the oligomeric hydrolyzed silicone oil has better adhesion to base materials such as PET and the like, and further has the effect of improving the adhesive force of the release agent by adjusting the surface tension of the release agent, so that the release agent is firmer in the coating process and is not easy to introduce impurities such as bubbles.
Controlling the reaction at lower temperatures and basic conditions helps control the hydrolysis rate of vinyltrimethoxysilane and glycidoxypropyltrimethoxysilane. Too strong acidity leads to too fast hydrolysis rate and difficulty in forming polycondensation products, thus having strong adverse effect on the release force of the release agent. And too high pH can cause the occurrence of polycondensation to be larger than the hydrolysis of silane, so that the two silanes form a polycondensation product with larger molecular weight, and obvious adverse effect is caused on the adhesive force.
In the control group a, the two silane coupling agents were added without reaction, and they participated in the curing reaction of the release agent during the reaction, but rather failed to exert the effect of the anchoring agent. Control B and control C each involved only one silane in the hydrolysis, and the oligomer formed from only one silane was inferior in adjusting tension and viscosity to the composite system formed from the two silanes, and thus was inferior in adhesion to the control examples.
Further, the addition of different silanes also had different effects on the properties of the release agent anchor, giving examples as shown in table 3.
Material selection in Table 3 and examples 16 to 23
The performance of the above examples in experiments 1 to 3 is shown in table 4.
Table 4 and Experimental results of examples 16 to 23
It is known from the above experiments that better adhesion can be achieved by using different ethyltrialkoxysilanes and glycidoxypropyltrialkoxysilanes, but when the viscosity of the ethylcellulose is too low, the adhesion is reduced to some extent. When the addition amount of the methyltrimethoxysilane is too large
Further, the release agent performance in the environment of long-term storage of food was measured, and the performance of experiment 4 was performed for examples 15 to 22, specifically, two environments were measured.
1. The release agent property was measured after 30 days of standing at a humidity of 100% and a temperature of 20 ℃.
2. The release agent property after being placed for 5 days at the temperature of 60 ℃ and the humidity of 60 +/-5 percent is measured.
The cross-cut test scale was further measured based on the above, and the measurement results are shown in table 5. In the following experiments, it is noted that in the residual stress ratio measurement, the pressure-sensitive adhesive was combined with a release agent and then placed in the above-mentioned environment, and in the cross-cut experimental measurement, the release agent was applied to a substrate and then directly placed in the above-mentioned environment without applying the pressure-sensitive adhesive.
Table 5 and Experimental results of examples 16 to 23
In the above experiment, it can be found that, in the food storage environment, the product of the present application has certain high temperature and high humidity resistance, and the stress attenuation thereof is small in the high temperature and high humidity environment. Wherein, when the vinyltrialkoxysilane is selected from vinyltrimethoxysilane and the glycidoxypropyltrialkoxysilane is selected from glycidoxypropyltrimethoxysilane, the residual stress has certain promotion effect.
After the methyl trimethoxy siloxane is added, the release agent in the application has obvious performance improvement, but still has obvious residual stress loss at high temperature, and the stress measurement of the pressure-sensitive adhesive is carried out before an aging experiment, so the reason probably lies in the intolerance of the pressure-sensitive adhesive to high-temperature and high-humidity environments, and the self aging of the pressure-sensitive adhesive is caused. The cross-cut experiment shows that the adhesive force of the release agent under high temperature and high humidity does not change obviously, and the methyl trimethoxy silane and other two silanes are hydrolyzed together to effectively improve the adhesive force of the anchoring agent, and meanwhile, the methyl trimethoxy silane is also beneficial to reducing the molecular migration between the release agent and the pressure-sensitive adhesive, the inactive groups on the surface of the methyl trimethoxy silane and the active ingredients in the pressure-sensitive adhesive can not react in the ultraviolet curing process, and the methyl trimethoxy silane has better affinity with a substrate (PET), so that the groups on the surface of the pressure-sensitive adhesive are beneficial to reducing the permeation of the release agent and the permeation of the base material, and the ratio of the residual stress is improved to a certain extent. However, too much methyltrimethoxysilane also leads to a reduction in the residual stress of the mold release.
Further, based on example 20, the amount of the anchoring agent in the release agent was adjusted, and the specific experimental results are shown in table 6.
TABLE 6 anchoring effect of example 23 at different loadings
It can be seen that the release agent in the application can achieve a good effect of improving the adhesive force within the range of 0.5-1.5, and has no obvious adverse effect on the release force and the profit loss of the pressure-sensitive adhesive. Further addition of an anchoring agent results in a certain loss of residual stress.
The above are preferred embodiments of the present application, and the scope of protection of the present application is not limited thereto, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. The anchoring agent for the release agent is characterized by being a product obtained by jointly hydrolyzing raw materials at least comprising a combination of vinyl trialkoxysilane and glycidoxypropyltrialkoxysilane, wherein the molar ratio of the vinyl trialkoxysilane to the glycidoxypropyltrialkoxysilane is 1: 1.0-1.2.
2. The anchoring agent for mold release according to claim 1, wherein said vinyltrialkoxysilane is any one of vinyltrimethoxysilane and vinyltriethoxysilane.
3. The anchoring agent for mold release according to claim 1, wherein said vinyltrialkoxysilane is vinyltrimethoxysilane.
4. The anchoring agent for mold release according to claim 1, wherein the ratio of the amount of the water system to the mass of the vinyltrialkoxysilane during hydrolysis is 8-10 mL: 1mol.
5. The anchoring agent for mold release according to claim 4, further comprising a water-insoluble cellulose, wherein the water-insoluble cellulose is ethyl cellulose ether N10 or ethyl cellulose N20.
6. The anchoring agent for mold release according to claim 4, wherein the mass of the water-insoluble cellulose is 0.05 to 0.5 times that of a product obtained by co-hydrolyzing a raw material of a combination of vinyltrialkoxysilane and glycidoxypropyltrialkoxysilane.
7. The anchoring agent for mold release according to claim 1, wherein vinyltrialkoxysiloxane and glycidoxypropyltrialkoxysilane are co-hydrolyzed under the following conditions: the reaction temperature is 40-60 ℃, the reaction time is 1-2 h, the pH is controlled to be 10.0-13.0 in the reaction process, and the solvent is removed after the reaction is finished.
8. The anchoring agent for mold release according to claim 7, wherein the pH is controlled to 12.2 to 12.8 during the reaction.
9. The anchoring agent for mold release according to claim 7, wherein methyltrimethoxysilane is further added during the reaction, and the molar ratio of methyltrimethoxysilane to vinyltrialkoxysilane is 0.01-0.05: 1.
10. The method of using the anchoring agent for mold release according to any of claims 1 to 9, characterized in that it is used for a reactive or non-reactive silicon-based mold release in an amount of 0.5 to 1.5% by mass of the total mass of the mold release.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567764A (en) * | 1995-07-28 | 1996-10-22 | Dow Corning Corporation | Curable silicone coatings containing alkoxy and alkenyl functional siloxanes |
| CN103154144A (en) * | 2010-10-14 | 2013-06-12 | 迈图高新材料日本合同公司 | Curable polyorganosiloxane composition |
| US20200207992A1 (en) * | 2017-07-31 | 2020-07-02 | Momentive Performance Materials Inc. | Curable surface-protective coating composition, processes for its preparation and application to a metallic substrate and resulting coated metallic substrate |
| CN111499870A (en) * | 2020-05-19 | 2020-08-07 | 深圳市康利邦科技有限公司 | Boiling-resistant organic silicon pressure-sensitive adhesive tackifier and preparation method thereof |
-
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- 2022-12-27 CN CN202211685336.7A patent/CN115975200B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5567764A (en) * | 1995-07-28 | 1996-10-22 | Dow Corning Corporation | Curable silicone coatings containing alkoxy and alkenyl functional siloxanes |
| CN103154144A (en) * | 2010-10-14 | 2013-06-12 | 迈图高新材料日本合同公司 | Curable polyorganosiloxane composition |
| US20200207992A1 (en) * | 2017-07-31 | 2020-07-02 | Momentive Performance Materials Inc. | Curable surface-protective coating composition, processes for its preparation and application to a metallic substrate and resulting coated metallic substrate |
| CN111499870A (en) * | 2020-05-19 | 2020-08-07 | 深圳市康利邦科技有限公司 | Boiling-resistant organic silicon pressure-sensitive adhesive tackifier and preparation method thereof |
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